US9704613B2 - Polymer composites with electromagnetic interference mitigation properties - Google Patents

Polymer composites with electromagnetic interference mitigation properties Download PDF

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US9704613B2
US9704613B2 US14/769,554 US201414769554A US9704613B2 US 9704613 B2 US9704613 B2 US 9704613B2 US 201414769554 A US201414769554 A US 201414769554A US 9704613 B2 US9704613 B2 US 9704613B2
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particles
polymeric matrix
composite
metal
lossy
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Dipankar Ghosh
Biplab K. Roy
Nitin S. Satarkar
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3M Innovative Properties Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C08K3/0033—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres

Definitions

  • This disclosure relates to polymer composites, especially polymer composites that are suitable for use as electromagnetic interference mitigaters.
  • Electromagnetic interference is a common issue encountered in electronic systems, such as electronic communications systems. Outside electromagnetic radiation is well known to induce undesirable currents in electronic components, thereby disrupting their normal operations. In order to protect against such effects, it is common to completely shield an electronic device or component via highly conductive enclosures, coatings, gaskets, adhesives sealants, wire sleeves, metal meshes or filters, and the like. These types of shields operate by reflecting the unwanted electromagnetic fields away from the sensitive component. Another form of protection is offered by electromagnetic absorbing materials. These are typically not highly conductive and operate by absorbing the unwanted electromagnetic energy and converting it to heat. Absorbers are widely used in radar and stealth applications. They are also commonly found inside of electronic devices where they are used to control electromagnetic emissions from the device. Electromagnetic absorbers can be classified as magnetic absorbers if they interact principally with the magnetic field component of an electromagnetic wave or as dielectric absorbers if the interact principally with the electric field component of the wave.
  • US Patent Publication No. 2010/0315105 describes an EMI shielding composite comprising a reactive organic compound and conductive filler that during the cure of the organic compound self-assembles into a three dimensional network of metal; and US Patent Publication No. 2011/0200740 (Ma et al.) which describes a carbon nanotube/polymer composite having EMI shielding effectiveness.
  • the polymer composite comprises a lossy polymeric matrix, ceramic particles dispersed within the polymeric matrix, and conductive particles dispersed within the polymeric matrix.
  • the lossy polymeric matrix may comprise a fluorocarbon-based polymer matrix, a chlorine-containing polymer matrix, an epoxy-based polymer matrix, a (meth)acrylate polymer matrix, a polyether polymer matrix, or a combination thereof.
  • the lossy polymeric matrix comprises a fluorocarbon-based polymer matrix or an epoxy-based polymer matrix.
  • the ceramic particles comprise metal oxide particles, metal nitride particles, metal carbide particles, metal sulfide particles, metal silicide particles, metal boride particles, particles of multiferroic compounds, mixed ceramic particles, chalcogenide glass particles, or a combination thereof.
  • the ceramic particles comprise metal oxide particles, especially copper oxide (CuO) particles.
  • the conductive particles comprise carbon black, carbon bubbles, carbon foams, graphene, carbon fibers, graphite, carbon nanotubes, metal particles and nanoparticles, metal alloy particles, metal nanowires, PAN fibers, conductive-coated particles, or a combination thereof.
  • the conductive particles comprise carbon black.
  • polymer composites that are electromagnetic interference mitigaters comprise a lossy polymeric matrix and copper oxide (CuO) particles dispersed within the polymeric matrix.
  • the lossy polymeric matrix may comprise a fluorocarbon-based polymer matrix, a chlorine-containing polymer matrix, an epoxy-based polymer matrix, a (meth)acrylate polymer matrix, a polyether polymer matrix, or a combination thereof.
  • the lossy polymeric matrix comprises a fluorocarbon-based polymer matrix or an epoxy-based polymer matrix.
  • FIG. 1 shows a plot of Dielectric Constant versus Frequency for the sample of Comparative Example C1.
  • FIG. 2 shows a plot of Loss Tangent versus Frequency for the sample of Comparative Example C1.
  • FIG. 3 shows a plot of Dielectric Constant versus Frequency for the sample of Example 1.
  • FIG. 4 shows a plot of Loss Tangent versus Frequency for the sample of Example 1.
  • FIG. 5 shows a plot of Dielectric Constant versus Frequency for the samples of Examples 2 and 3.
  • FIG. 6 shows a plot of Loss Tangent versus Frequency for the samples of Examples 2 and 3.
  • FIG. 7 shows a plot of Dielectric Constant versus Frequency for the sample of Example 4.
  • FIG. 8 shows a plot of Loss Tangent versus Frequency for the sample of Example 4.
  • FIG. 9 shows a plot of Dielectric Constant versus Frequency for the samples of Comparative Examples C2-C5.
  • FIG. 10 shows a plot of Loss Tangent versus Frequency for the samples of Comparative Examples C2-C5.
  • FIG. 11 shows a plot of Dielectric Constant versus Frequency for the samples of Examples 5-7.
  • FIG. 12 shows a plot of Loss Tangent versus Frequency for the samples of Examples 5-7.
  • FIG. 13 shows a plot of Dielectric Constant versus Frequency for the samples of Examples 8-10.
  • FIG. 14 shows a plot of Loss Tangent versus Frequency for the samples of Examples 8-10.
  • FIG. 15 shows a plot of Dielectric Constant versus Frequency for the samples of Comparative Examples C6 and C7.
  • FIG. 16 shows a plot of Loss Tangent versus Frequency for the samples of Comparative Examples C6 and C7.
  • FIG. 17 shows a plot of Dielectric Constant versus Frequency for the samples of Examples 11 and 12.
  • FIG. 18 shows a plot of Loss Tangent versus Frequency for the samples of Examples 11 and 12.
  • FIG. 19 shows a plot of Dielectric Constant versus Frequency for the samples of Examples 13 and 14.
  • FIG. 20 shows a plot of Loss Tangent versus Frequency for the samples of Examples 13 and 14.
  • EMI electromagnetic interference
  • composite refers to a material in which two or more materials coexist without chemical interaction, and one or more phases can be discrete or continuous.
  • the term “lossy polymeric matrix” as used herein refers to polymeric matrix that has a dielectric loss tangent in the range from 0.005-0.50 or even 0.01-0.30 over the frequency range of interest.
  • the dielectric loss tangent typically referred to as tan ⁇ , is a frequency dependent parameter of a dielectric material that quantifies its inherent dissipation of electromagnetic energy.
  • polymer and polymeric material refer to both materials prepared from one monomer such as a homopolymer or to materials prepared from two or more monomers such as a copolymer, terpolymer, or the like.
  • polymerize refers to the process of making a polymeric material that can be a homopolymer, copolymer, terpolymer, or the like.
  • copolymer and copolymeric material refer to a polymeric material prepared from at least two monomers.
  • room temperature and “ambient temperature” are used interchangeably to mean temperatures in the range of 20° C. to 25° C.
  • fluorocarbon-based refers to a material that is fluorinated. Typically, the fluorocarbon-based materials of this disclosure are highly fluorinated.
  • fluorinated when used in conjunction with polymer, monomer, or group associated with a polymer or a monomer, refers to having at least one hydrogen atom replaced with a fluorine atom.
  • highly fluorinated refers to polymers, monomers, or groups where many hydrogen atoms have been replaced with fluorine atoms, in some cases at least half of the hydrogen atoms have been replaced by fluorine atoms, and in other cases, nearly all of the hydrogen atoms have been replaced with fluorine atoms.
  • (meth)acrylate refers to both acrylate and methacrylate materials.
  • epoxy refers to reactive group that is three membered ring including two carbon atoms and an oxygen atom, commonly referred to as an “oxirane ring”.
  • epoxy resin as used herein is in agreement with the generally understood usage for this term in the art and is used to describe curable materials containing one or more epoxy groups.
  • EMI mitigating polymeric composites that comprise a lossy polymeric matrix and one or more type of added particles.
  • the EMI mitigating polymeric composite comprises a lossy polymeric matrix, ceramic particles dispersed within the polymeric matrix, and conductive particles dispersed within the polymeric matrix.
  • the EMI mitigating polymeric composite comprises a lossy polymeric matrix and copper oxide (CuO) particles dispersed within the polymeric matrix. Both of these types of EMI mitigating polymeric composites are discussed in greater detail below.
  • the composite mitigates electromagnetic interference in the 100 MegaHertz-100 GigaHertz range, more typically the 100 MegaHertz-70 GigaHertz range, or even the 1-20 GigaHertz range. These materials are also expected to mitigate electromagnetic interference in lower frequency ranges as well, such as in the kiloHertz and lower MegaHertz bands.
  • EMI mitigating polymeric composites comprising a polymeric matrix having a loss tangent of from 0.005-0.50, or even 0.01-0.30, ceramic particles dispersed within the polymeric matrix, and conductive particles dispersed within the polymeric matrix.
  • the EMI mitigating polymeric composites comprise a polymeric matrix having a loss tangent of from 0.005-0.50, or even 0.01-0.30.
  • Any polymeric matrix that has the desired intrinsic dielectric loss properties may be suitable as the polymeric matrix for this disclosure.
  • suitable polymeric matrix materials are: materials containing halocarbon groups, that is to say polymeric material that contain C—X, bonds where X is, for example, a fluorine atom or a chlorine atom, such materials include fluorocarbon-based polymers and chlorine-containing polymers; epoxy-based materials, including epichlorohydrin polymers and copolymers as well as epoxy resin polymers; (meth)acrylate polymers and copolymers; and polyether polymers and copolymers.
  • Particularly suitable polymeric matrix materials are epoxy-based polymeric matrices and fluorocarbon-based polymeric matrices.
  • a key component contributing to the dielectric loss in polymers is associated with the relaxation of the short polar segments containing groups with high dipole moments.
  • Some examples of such polarized bonds include: C—OR groups where R is a hydrogen atom or an alkyl or aryl group; C—X groups where X is a halogen atom such as a fluorine or chlorine atom; and C—NR 1 R 2 where each R 1 and R 2 group is independently a hydrogen atom, an alkyl group or an aryl group.
  • the polar segments can either be a part of the backbone structure or on a side chain.
  • the degree of crystallinity is another parameter that affects the dielectric loss in polymers, with less crystalline polymeric matrices having greater dielectric loss, because increased crystallinity reduces the degree of freedom of movement of the polymer chain.
  • amorphous polymer matrices have higher free volumes, which enhance the ease of polymer segment rotation and increases dielectric loss due to absorption of electromagnetic energy.
  • polymeric matrices with greater amorphous regions, and consequently lower crystallinity have higher dielectric loss, i.e. are “more lossy”.
  • the degree of crystallinity in polymers can be controlled by polymer composition and by the choice of processing conditions.
  • the mobility of the polymer chains is also affected by the glass transition temperature. Even amorphous polymers with high glass transition temperatures (that is to say T g values that are greater than the use temperature, generally ambient temperature or room temperature) have restricted mobility at the use temperature. Therefore, polymeric matrices that have T g values that are lower than the use temperature (generally room temperature) are more lossy than polymer matrices with T g values that are higher than the use temperature.
  • the T g of the matrix can also be affected by the use of additives. For example, the T g of the matrix can be lowered by the addition of plasticizers.
  • the degree of crosslinking in the matrix is especially important in cured polymeric systems such as cured epoxy resin systems.
  • a higher level of crosslinking adversely affects chain segment mobility, and thus lowers the dielectric loss of the matrix.
  • lower levels of crosslinking are generally desirable for cured polymeric systems.
  • the lossiness of polymeric systems are also affected by factors such as the degree of branching (as branching tends to break up crystallinity), the nature of the resulting end-groups (whether polar or non-polar), the presence of impurities or additives such as unreacted monomers, solvents such as water, processing aids such anti-oxidants, and the like.
  • suitable polymeric matrix materials are: materials containing halocarbon groups, that is to say polymeric material that contain C—X, bonds where X is, for example, a fluorine atom or a chlorine atom; epoxy-based materials, including epichlorohydrin polymers and copolymers as well as epoxy resin polymers; (meth)acrylate polymers and copolymers; and polyether polymers and copolymers.
  • Examples of polymeric materials containing halocarbon groups include a wide range of chlorine-containing and fluorine-containing polymers.
  • suitable chlorine-containing polymers include polyvinyl chloride polymers (PVCs) and polyvinylidene chloride polymers (PVDC).
  • PVC polymers contain polar C—Cl groups, but tend to have relatively high T g values (up to 95° C.) and thus show only moderate dielectric loss properties.
  • PVDC polymers on the other hand not only contain polar C—Cl groups, but also have relatively low T g values ( ⁇ 17° C.).
  • a wide variety of fluorine-containing polymers are suitable.
  • the suitable fluorine-containing polymers are polyvinylidene fluoride (PVDF) polymers and copolymers.
  • PVDF polymers have a very low T g value ( ⁇ 65° C.).
  • Particularly suitable examples of PVDF and other fluorine-containing polymers including copolymers prepared from the fluorocarbon-based monomers tetrafluoroethylene (TFE), hexafluoropropylene (HFP), as well as vinylidene fluoride (VDF) are described in greater detail below.
  • Examples of epoxy-based polymeric matrix materials include a wide range of epichlorohydrin-based polymers and epoxy resin based polymers.
  • Examples of epichlorohydrin-based polymers include both poly-epichlorohydrin such as the epichlorohydin homopolymer commercially available from Zeon Chemical as HYDRIN H (CO), and epichlorohydrin copolymers such as the copolymer of epichlorohydrin and ethylene oxide commercially available from Zeon Chemical as HYDRIN C (ECO), and the terpolymer of epichlorohydrin, ethylene oxide, and allyl glycidyl ether commercially available from Zeon Chemical as HYDRIN T.
  • a wide range of curable epoxy resins are suitable, including ones based upon bisphenol-A, bisphenol-F, and phenol novolacs. Particularly suitable epoxy resin systems are described in greater detail below.
  • Suitable (meth)acrylate polymers and copolymers include polymethyl acrylate polymers (PMA) and polymethyl methacrylate polymers (PMMA) which demonstrate a high degree of amorphous content, polar groups from the (meth)acrylate functionality, and generally show moderate dielectric loss at room temperature.
  • PMA polymethyl acrylate polymers
  • PMMA polymethyl methacrylate polymers
  • Polyether polymers and copolymers tend to have desirable dielectric loss values because the C—O—C bonds of the backbone not only are polar groups as described above but they also have a great deal of flexibility. Additionally, polyether polymers and copolymers have low T g values (generally ⁇ 70° C.). A wide variety of polyether polymers and copolymers are commercially available including, for example, polyethylene oxide polymers and copolymers, and polypropylene oxide polymers and copolymers.
  • epoxy-based polymeric matrices and fluorocarbon-based polymeric matrices are particularly suitable polymeric matrix materials. These reasons include not only the desirable lossy properties of the polymeric matrices, but also stability over time, availability of materials, handling properties, and the like.
  • suitable epoxy-based polymeric matrices include those prepared from epoxy resins based upon bisphenol-A, bisphenol-F, phenol novolacs, or combinations thereof.
  • suitable epoxy resins based upon bisphenol-A include: EPON 828 (liquid epoxy resin) and EPON 1001F (solid epoxy resin), commercially available from Momentive Specialty Chemicals, Columbus, Ohio; DER 6508 (high molecular weight epoxy resin) commercially available from Dow Chemical Company, Midland Mich.; and EPDXICURE resin (a low molecular weight epoxy resin) commercially available from Buehler, Lake Bluff, Ill.
  • An example of a suitable bisphenol-F epoxy resin is EPON 862 (a low molecular weight epoxy resin) commercially available from Momentive Specialty Chemicals, Columbus, Ohio
  • suitable epoxy resins based upon phenol novolacs include: EPON 1050, commercially available from Momentive Specialty Chemicals, Columbus, Ohio; and ARALDITE ECN 1299 commercially available from Huntsman Advanced Materials Americas, Inc., The Woodlands, Tex. Mixtures or epoxy resins can also be used.
  • the epoxy resins can be cured using a wide variety of curing agents including amine-based curing agents, phenolic curing agents, and anhydride-based curing agents.
  • fluorocarbon-based polymeric matrices comprise fluorocarbon-based polymers.
  • the fluorocarbon-based polymeric matrix comprises a single fluorocarbon-based polymer, in other embodiments, the fluorocarbon-based polymeric matrix comprises a mixture of fluorocarbon-based polymers.
  • suitable fluorocarbon-based polymers include those copolymers prepared from the fluorocarbon-based monomers tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF). Examples of such polymers are described in U.S. Pat. No. 6,310,141 (Chen et al.). Examples of suitable fluorocarbon-based polymers include, for example, terpolymers of 20-60 wt. % TFE, 30-50 wt. % HFP, and 10-40% VDF. These terpolymers are commercially available from 3M Corp, St. Paul, Minn. under the trade name “THV”.
  • HTE hexafluoropropylene-tetrafluoroethylene-ethylene
  • ETFE ethylene-tetrafluoroethylene
  • FEP hexafluoropropylene-tetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoro(alkoxy alkane) copolymers
  • VDF-containing fluorocarbon-based polymers examples include the materials THV 200, THV 400, THV 500G commercially available from 3M Corp, St. Paul, Minn.; KYNAR 720, KYNAR 740, KYNAR 1000HD, and KYNAR ADX commercially available from ARKEMA, Philadelphia, Pa.; HYLAR 700 commercially available from Ausimont USA Inc., Morristown, N.J.; and FLUOREL FC-2178 commercially available from 3M Corp, St. Paul, Minn. Particularly useful are the poly-VDF polymers KYNAR 720, KYNAR 740, KYNAR 1000HD, and KYNAR ADX commercially available from ARKEMA, Philadelphia, Pa.
  • some embodiments of the EMI mitigating polymeric composites also comprise ceramic particles dispersed within the polymeric matrix.
  • These ceramic particles are lossy dielectric ceramic particles.
  • a wide range of ceramic particles are suitable. Suitable ceramic particles include metal oxide particles, metal nitride particles, metal carbide particles, metal sulfide particles, metal silicide particles, metal boride particles, particles of multiferroic compounds, mixed ceramic particles, chalcogenide glass particles, or a combination thereof. Each of these materials is described in greater detail below.
  • the particles range in size from an average particle size of 50 nanometers-50 micrometers, more typically 1-10 micrometers and the ceramic particles are generally present in an amount 10-90 weight %, more typically 10-80 weight %.
  • metal oxide particles are suitable for use in the composites of this disclosure.
  • suitable metal oxide particles include doped and undoped particles of tin oxide, iron oxide (ferrous or ferric oxide), zinc oxide, manganese oxide, lead oxide, nickel oxide, cobalt oxide, silver oxide, antimony oxide, and copper oxide (CuO). Mixtures of metal oxide particles are also suitable.
  • metal nitride particles examples include doped and undoped particles of tantalum nitride, titanium nitride, vanadium nitride, and zirconium nitride. Mixtures of metal nitride particles are also suitable.
  • metal carbide particles examples include doped and undoped particles of tungsten carbide, niobium carbide, titanium carbide, vanadium carbide, molybdenum carbide, silicon carbide, zirconium carbide, boron carbide, and titanium silicon carbide. Mixtures of metal carbide particles are also suitable.
  • metal sulfide particles examples include doped and undoped particles of copper sulfide, silver sulfide, iron sulfide, nickel sulfide, cobalt sulfide, lead sulfide, and zinc sulfide. Mixtures of metal sulfide particles are also suitable.
  • metal silicide particles examples include doped and undoped particles of chromium silicide, molybdenum silicide, cobalt silicide, vanadium silicide, tungsten silicide, and titanium silicide. Mixtures of metal silicide particles are also suitable.
  • metal boride particles examples include doped and undoped particles of chromium boride, molybdenum boride, titanium boride, zirconium boride, niobium boride, and tantalum boride. Mixtures of metal boride particles are also suitable.
  • particles of multiferroic compounds examples include doped and undoped particles of bismuth ferrite (BiFeO 3 ), bismuth manganate (BiMnO 3 ), and rare earth-iron oxides (MFe 2 O 4 where M is a rare earth element, such as, for example, LuFe 2 O 4 ). Mixtures of particles of multiferroic compounds are also suitable.
  • mixed ceramic particles include particles with a mixture of metal or metalloid elements. Suitable examples include doped and undoped particles of silicon carbide and beryllium oxide, silicon carbide and aluminum nitride, copper oxide (CuO) and aluminum oxide, aluminum nitride and glassy carbon, and Si—Ti—C—N ceramics.
  • chalcogenide glass particles include glassy materials based on As—Ge—Te and Se—Ge—Te.
  • metal oxide particles especially copper oxide (CuO).
  • some embodiments of this disclosure include composites that also comprise conductive particles dispersed within the polymeric matrix.
  • conductive particles include carbon black, carbon bubbles, carbon foams, graphene, carbon fibers, graphite, graphite nanoplatelets, carbon nanotubes, metal particles and nanoparticles, metal alloy particles, metal nanowires, PAN fibers, conductive-coated particles (such as, for example, metal coated glass particles), or a combination thereof.
  • carbon black is particularly suitable.
  • the conductive particles range in size from an average particle size of 5 nanometers-20 micrometers, more typically 5-500 nanometers and the conductive particles are generally present in an amount 0.05-20 weight %, more typically 0.05-3 weight %.
  • particularly suitable embodiments of composites of this disclosure include those where the polymeric matrix comprises a terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride, the ceramic particles comprise copper oxide (CuO) particles, and the conductive particles comprise carbon black.
  • the polymeric matrix comprises a vinylidene fluoride polymer (PVDF), the ceramic particles comprise copper oxide (CuO) particles, and the conductive particles comprise carbon black.
  • composites of this disclosure include those where the polymeric matrix comprises epoxy resins including bisphenol-A epoxy resins, bisphenol-F epoxy resins, or phenol novolac epoxy resins, or a combination thereof, the ceramic particles comprise copper oxide (CuO) particles, and the conductive particles comprise carbon black.
  • epoxy resins including bisphenol-A epoxy resins, bisphenol-F epoxy resins, or phenol novolac epoxy resins, or a combination thereof
  • the ceramic particles comprise copper oxide (CuO) particles
  • the conductive particles comprise carbon black.
  • EMI mitigating polymeric composites comprising a lossy polymeric matrix and copper oxide (CuO) particles dispersed within the polymeric matrix.
  • the composite mitigates electromagnetic interference in the 100 MegaHertz-100 GigaHertz range, more typically the 100 MegaHertz-70 GigaHertz range, or even the 1-20 GigaHertz range.
  • CuO copper oxide
  • these materials are also expected to mitigate electromagnetic interference in lower frequency ranges as well, such as in the kiloHertz and lower MegaHertz bands.
  • the EMI mitigating polymeric composites comprise a polymeric matrix having a loss tangent of from 0.005-0.50, or even 0.01-0.30.
  • Any suitable polymeric matrix that has the desired intrinsic dielectric loss properties may be suitable as the polymeric matrix for this disclosure, such as those described above.
  • the suitable polymeric matrix materials are epoxy-based polymeric matrices and fluorocarbon-based polymeric matrices.
  • suitable epoxy-based polymeric matrices include those prepared from epoxy resins based upon bisphenol-A, bisphenol-F, phenol novolacs, or combinations thereof.
  • suitable epoxy resins based upon bisphenol-A include: EPON 828 (liquid epoxy resin) and EPON 1001F (solid epoxy resin), commercially available from Momentive Specialty Chemicals, Columbus, Ohio; DER 6508 (high molecular weight epoxy resin) commercially available from Dow Chemical Company, Midland Mich.; and EPDXICURE resin (a low molecular weight epoxy resin) commercially available from Buehler, Lake Bluff, Ill.
  • An example of a suitable bisphenol-F epoxy resin is EPON 862 (a low molecular weight epoxy resin) commercially available from Momentive Specialty Chemicals, Columbus, Ohio
  • suitable epoxy resins based upon phenol novolacs include: EPON 1050, commercially available from Momentive Specialty Chemicals, Columbus, Ohio; and ARALDITE ECN 1299 commercially available from Huntsman Advanced Materials Americas, Inc., The Woodlands, Tex. Mixtures or epoxy resins can also be used.
  • the epoxy resins can be cured using a wide variety of curing agents including amine-based curing agents, phenolic curing agents, and anhydride-based curing agents.
  • fluorocarbon-based polymeric matrices comprise fluorocarbon-based polymers.
  • the fluorocarbon-based polymeric matrix comprises a single fluorocarbon-based polymer, in other embodiments, the fluorocarbon-based polymeric matrix comprises a mixture of fluorocarbon-based polymers.
  • suitable fluorocarbon-based polymers include those copolymers prepared from the fluorocarbon-based monomers tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF). Examples of such polymers are described in U.S. Pat. No. 6,310,141 (Chen et al.). Examples of suitable fluorocarbon-based polymers include, for example, terpolymers of 20-60 wt. % TFE, 30-50 wt. % HFP, and 10-40% VDF. These terpolymers are commercially available from 3M Corp, St. Paul, Minn. under the trade name “THV”.
  • HTE hexafluoropropylene-tetrafluoroethylene-ethylene
  • ETFE ethylene-tetrafluoroethylene
  • FEP hexafluoropropylene-tetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoro(alkoxy alkane) copolymers
  • VDF-containing fluorocarbon-based polymers examples include the materials THV 200, THV 400, THV 500G commercially available from 3M Corp, St. Paul, Minn.; KYNAR 720, KYNAR 740, KYNAR 1000HD, and KYNAR ADX commercially available from ARKEMA, Philadelphia, Pa.; HYLAR 700 commercially available from Ausimont USA Inc., Morristown, N.J.; and FLUOREL FC-2178 commercially available from 3M Corp, St. Paul, Minn. Particularly useful are the poly-VDF polymers KYNAR 720, KYNAR 740, KYNAR 1000HD, and KYNAR ADX commercially available from ARKEMA, Philadelphia, Pa.
  • Suitable copper oxide (CuO) particles typically range in size from an average particle size of 50 nanometers-50 micrometers, more typically 1-10 micrometers and the copper oxide (CuO) particles are generally present in an amount 10-90 weight %, more typically 10-80 weight %.
  • E8363C Air Coax Test Air coax test fixture available from Damaskos, Inc., Concordville, PA, model Fixture no. 100T Twin Screw Twin screw extruder, available from B&P Process Equipment and Systems Extruder LLC, Saginaw, MI, model no. MP-2019 15:1 Annular Steel Annular steel mold, outer diameter 2.54 cm, inner diameter 1.10 cm, custom- Mold manufactured Manual Manual hydraulic press, available from Carver, Inc., Wabash, IN, model no. Hydraulic Press 32000 Milling Machine Milling machine, available under the trade designation BRIDGEPORT from Hardinge, Inc., Elmira, NY Carbide Tool Carbide tool, available from Travers Tool Company, Inc. Flushing, NY, tool no. BL5-C6
  • Epoxy Resin Compositions were prepared and used:
  • Epoxy Resin System-1 was a mixture of 100.00 parts by weight epoxy resin (EPDXICURE Resin (low molecular weight bisphenol A-based epoxy resin, commercially available from Buehler, Lake Bluff, Ill.), and 18.00 phr epoxy curing agent (EPDXICURE Hardener (a mixture of aliphatic amines) commercially available from Buehler, Lake Bluff, Ill.).
  • EPDXICURE Resin low molecular weight bisphenol A-based epoxy resin, commercially available from Buehler, Lake Bluff, Ill.
  • EPDXICURE Hardener a mixture of aliphatic amines
  • Epoxy Resin System-2 was a mixture of 100.00 parts by weight epoxy resin (EPON 862, low molecular weight bisphenol F-based epoxy resin, commercially available from Momentive Specialty Chemicals, Inc., Columbus, Ohio), and 46.50 phr epoxy curing agent (EPIKURE 3233 (polyoxypropylenetriamene) commercially available from Momentive Specialty Chemicals, Inc., Columbus, Ohio).
  • EPON 862 low molecular weight bisphenol F-based epoxy resin, commercially available from Momentive Specialty Chemicals, Inc., Columbus, Ohio
  • EPIKURE 3233 polyoxypropylenetriamene
  • Epoxy Resin System-3 was a mixture of 100.00 parts by weight epoxy resin (D.E.R. 6508, high molecular weight bisphenol A-based epoxy resin, commercially available from The Dow Chemical Company, Midland, Mich.), and a curative mixture of: a) 8.46 phr epoxy curing agent, (D.E.H. 85 (phenolic) commercially available from The Dow Chemical Company, Midland, Mich.); b) 2.59 phr epoxy curing agent, (DYHARD 100 (amine) commercially available from AlzChem LLC, Atlanta, Ga.); and c) 1.32 phr epoxy curing accelerator, (EPIKURE P-100 commercially available from Momentive Specialty Chemicals, Inc., Columbus, Ohio).
  • D.E.R. 6508 high molecular weight bisphenol A-based epoxy resin, commercially available from The Dow Chemical Company, Midland, Mich.
  • Epoxy Resin System-4 was a mixture of 100.00 parts by weight epoxy resin (ARALDITE ECN 1299 from Huntsman Advanced Materials Americas, Inc., The Woodlands, Tex.), and a curative mixture of: a) 68.48 phr epoxy curing agent, (BTDA, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (anhydride), commercially available from Evonik Industries, Essen, Germany); and b) 1.70 phr epoxy curing accelerator, (EPIKURE P-100 commercially available from Momentive Specialty Chemicals, Inc., Columbus, Ohio).
  • ARALDITE ECN 1299 from Huntsman Advanced Materials Americas, Inc., The Woodlands, Tex.
  • Primed PI film was prepared by cleaning the PI Film with ethanol, drying, applying a of a very thin coating of the Primer by rubbing the PI Film with a wiper soaked with the Primer, allowing the primer to dry for at least 1 hour in air, and then drying overnight in an air-ventilated hood.
  • a sample of the PVDF polymer with no fillers was prepared and analyzed.
  • a predetermined quantity of the PVDF polymer was placed in a glass beaker and heated to a temperature of 250° C. for 10 minutes on a hot plate.
  • the resulting fluid was poured onto an Aluminum Plate and hot pressed at a temperature of 175° C. and a pressure of 6 metric tons for 15 minutes using the Laboratory Press.
  • the hot pressed polymer sheet was allowed to cool to room temperature and cut into a toroid or doughnut-shaped sample having an outer diameter of 2.54 cm and an inner diameter of 1.10 cm, with a thickness of 1-2 mm.
  • Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture.
  • FIGS. 1 and 2 illustrating the dielectric constant vs. the frequency and the loss tangent vs. the frequency, respectively, of the sample.
  • the dielectric constant of the sample is about 3.0 over the frequency range ( FIG. 1 )
  • the loss tangent is about 0.1 in the low frequency range ( FIG. 2 ), demonstrating that PVDF polymers are intrinsically lossy polymer materials.
  • a sample of the PVDF polymer with 16.25 wt % CuO Filler and 0.34 wt % CB Filler-1 was prepared and analyzed.
  • the CuO Filler and CB Filler-1 were blended with PVDF polymer in a glass beaker at a temperature of 250° C. for 10 minutes on a hot plate.
  • DMF solvent was used to dissolve the PVDF polymer, and a drop of FS dispersant was added to the mixture.
  • the resulting mixture was poured onto the Aluminum Plate and hot pressed at a temperature of 200° C. and a pressure of 6 metric tons for 15 minutes using the Laboratory Press.
  • the hot pressed polymer composite was then allowed to cool to room temperature and cut into a toroid or doughnut-shaped sample having an outer diameter of 2.54 cm and an inner diameter of 1.10 cm, and a thickness of 1-2 mm.
  • Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture. The results are shown in FIGS. 3 and 4 , illustrating the dielectric constant vs. the frequency and the loss tangent vs. the frequency, respectively, of the sample.
  • CuO Filler particles were ground manually in a mortar and pestle, crushed in a high speed mechanical grinder for 5 minutes, and dried for at least 4 hours at 60° C.
  • Dispersions were made by adding small portions of CuO Filler, speed mixing using a high speed mixer, ultrasonication for 5 minutes at a temperature of 60° C. using an ultrasonicator, and heating at a temperature of 65° C. using the hot plate.
  • the suspension was coated on primed PI Film using a wet film applicator with a 375 micrometer (15 mil) clearance setting.
  • the coated sample was placed in the oven preheated at a temperature of 250° C. After 30 minutes, the oven was shut down and the sample was allowed to air cool.
  • Example 4 CuO Filler particles were ground and crushed as described above, and CB Filler-2 pellets were ground in a high speed mechanical grinder for 5 minutes. The resulting powders were dried for at least 4 hours at 60° C.
  • a dispersant stock solution was prepared by dissolving 1.95 grams of FS dispersant in 4 ml of DMF solvent.
  • a PVDF polymer solution was prepared by dissolving 3 g or PVDF in 9 ml of DMF solvent by heating overnight at 65° C. in a closed vial.
  • a dispersion was made by adding small portions of CuO Filler, and CB Filler-2 ground in a mortar and pestle with 150 microliters of dispersant stock solution, and speed mixing using a high speed mixer, ultrasonication for 5 minutes at a temperature of 60° C. using an ultrasonicator, and heating at a temperature of 65° C. using the hot plate.
  • the suspension was coated on primed PI Film using a wet film applicator with a 375 micrometer (15 mil) clearance setting.
  • the coated sample was placed in the oven preheated at a temperature of 250° C. After 30 minutes, the oven was shut down and the sample was allowed to air cool.
  • Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture. The results are shown in FIGS. 7 and 8 .
  • Comparative Example C2 the liquid epoxy resin system of Synthesis Example S1
  • Comparative Example C3 the liquid epoxy resin system of Synthesis Example S2
  • the epoxy resin and the curing agent were mixed in the high speed mixer and cast in aluminum pans having a 57 mm diameter.
  • Comparative Example C2 was cured at a temperature of 65° C. for 2 hours in an oven.
  • Comparative Example C3 was cured at a temperature of 60° C. for 2 hours followed by post-curing at a temperature of 100° C. for 2 hours.
  • the cured material was machined into a toroid or doughnut-shaped sample having an outer diameter of 2.54 cm and an inner diameter of 1.10 cm using a Milling Machine with a Carbide Tool.
  • the epoxy resin and the curing agent were compounded using a Twin Screw Extruder at a temperature of 110° C.
  • the extruded material was cured at a temperature of 110° C. overnight, and post-cured at a temperature of 200° C. for 15 minutes.
  • the cured material was machined into a toroid shaped sample using method as for Comparative Examples C2 and C3 above.
  • Comparative Example C5 the extruded material was crushed into powder using a high speed mechanical grinder. The powder was pressed into a toroid or doughnut-shaped pellet having an outer diameter of 2.54 cm and an inner diameter of 1.10 cm using an Annular Steel Mold in a Manual Hydraulic Press at 30,000 psi pressure, and cured in the oven at a temperature of 200° C. for 20 minutes. The samples had a thickness of 2-5 mm. Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture. The results are shown in FIGS. 9 and 10 , illustrating the dielectric constant vs. the frequency and the loss tangent vs. the frequency, respectively, of Comparative Example C2 (901, 1001), Comparative Example C3 (902, 1002), Comparative Example C4 (903, 1003), and Comparative Example C5 (904, 1004).
  • Example 5 the liquid epoxy resin system of Synthesis Example S1 with 64.8 wt % CuO Filler
  • Example 6 the liquid epoxy resin system of Synthesis Example S2 with 65.4 wt % CuO Filler
  • the epoxy resin and CuO Filler were mixed in a high speed mixer, the curing agent was added and mixed, and the resulting mixture cast in aluminum pans having a 57 mm diameter.
  • Example 5 was cured at a temperature of 65° C. for 2 hours in an oven.
  • Example 6 was cured at a temperature of 60° C. for 2 hours followed by post-curing at a temperature of 100° C. for 2 hours.
  • the cured material was machined into a toroid or doughnut-shaped sample having an outer diameter of 2.54 cm and an inner diameter of 1.10 cm using a Milling Machine with a Carbide Tool.
  • Example 7 the solid epoxy resin system of Synthesis Example S3 with 63.7 wt % CuO Filler
  • the epoxy resin, CuO Filler, and the curing agent were compounded using a Twin Screw Extruder at a temperature of 110° C.
  • the extruded material was cured at a temperature of 110° C. overnight, and post-cured at a temperature of 200° C. for 15 minutes.
  • the cured material was machined into a toroid shaped sample using method as for Comparative Examples C2 and C3 above.
  • the samples had a thickness of 2-5 mm.
  • Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture. The results are shown in FIGS. 11 and 12 , illustrating the dielectric constant vs. the frequency and the loss tangent vs. the frequency, respectively, of Example 5 (1101, 1201), Example 6 (1102, 1202), and Example 7 (1103, 1203).
  • Example 8 the liquid epoxy resin system of Synthesis Example S1 with 64.8 wt % CuO Filler and 0.55 wt % CB Filler-2
  • Example 9 the liquid epoxy resin system of Synthesis Example S2 with 65.2 wt % CuO Filler and 0.55 wt % CB Filler-2
  • the epoxy resin, CuO Filler, CB Filler-2, and 5 wt % Surfactant based on the weight of CB Filler-2 were mixed in a high speed mixer, the curing agent was added and mixed, and the resulting mixture cast in aluminum pans having a 57 mm diameter.
  • Example 5 was cured at a temperature of 65° C. for 2 hours in an oven.
  • Example 6 was cured at a temperature of 60° C. for 2 hours followed by post-curing at a temperature of 100° C. for 2 hours.
  • the cured material was machined into a toroid or doughnut-shaped sample having an outer diameter of 2.54 cm and an inner diameter of 1.10 cm using a Milling Machine with a Carbide Tool.
  • Example 10 the solid epoxy resin system of Synthesis Example S3 with 63.5 wt % CuO Filler and 0.36 wt % CB Filler-2
  • the epoxy resin, fillers, and the curing agent were compounded using a Twin Screw Extruder at a temperature of 110° C.
  • the extruded material was cured at a temperature of 110° C. overnight, and post-cured at a temperature of 200° C. for 15 minutes.
  • the cured material was machined into a toroid shaped sample using method as for Comparative Examples C2 and C3 above.
  • the samples had a thickness of 2-5 mm.
  • Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture. The results are shown in FIGS. 13 and 14 , illustrating the dielectric constant vs. the frequency and the loss tangent vs. the frequency, respectively, of Example 8 (1301, 1401), Example 9 (1302, 1402), and Example 10 (1303, 1403).
  • Comparative Examples C6 and C7 are epoxy resin systems with no fillers
  • Examples 11 and 12 are epoxy resin systems with CuO Filler
  • Examples 13 and 14 are epoxy resin systems with CuO Filler and CB Filler-2.
  • Comparative Example C6 the liquid epoxy resin system of Synthesis Example S1
  • Comparative Example C7 the liquid epoxy resin system of Synthesis Example S2
  • the epoxy resin and the curing agent were mixed in a high speed mixer. Once a uniform suspension with a viscosity suitable for coating was obtained, the suspension was coated on primed PI Film using a wet film applicator with a 125 micrometer (5 mil) clearance setting.
  • Comparative Example C6 was cured at a temperature of 65° C. for 2 hours in an oven. Comparative Example C7 was cured at a temperature of 60° C. for 2 hours followed by post-curing at a temperature of 100° C. for 2 hours. The cured coating layer has a thickness of 80-100 micrometers.
  • Example 11 the liquid epoxy resin system of Synthesis Example S1 with 70.5 wt % CuO Filler
  • Example 12 the liquid epoxy resin system of Synthesis Example S2 with 70.8 wt % CuO Filler
  • the epoxy resin and CuO Filler were mixed in a high speed mixer, the curing agent was added and mixed.
  • Example 11 was cured at a temperature of 65° C. for 2 hours in an oven.
  • Example 12 was cured at a temperature of 60° C. for 2 hours followed by post-curing at a temperature of 100° C. for 2 hours.
  • the cured coating layer has a thickness of 80-100 micrometers.
  • Example 13 the liquid epoxy resin system of Synthesis Example S1 with 64.8 wt % CuO Filler and 0.55 wt % CB Filler-2) and Example 14 (the liquid epoxy resin system of Synthesis Example S2 with 65.2 wt % CuO Filler and 0.55 wt % CB Filler-2), the epoxy resin, CuO Filler, and CB Filler-2 were mixed in a high speed mixer, the curing agent was added and mixed. Once a uniform suspension with a viscosity suitable for coating was obtained, the suspension was coated on primed PI Film using a wet film applicator with a 125 micrometer (5 mil) clearance setting. Example 13 was cured at a temperature of 65° C. for 2 hours in an oven.
  • Example 14 was cured at a temperature of 60° C. for 2 hours followed by post-curing at a temperature of 100° C. for 2 hours.
  • the cured coating layer has a thickness of 80-100 micrometers.
  • Complex dielectric properties were calculated over the frequency range from S-parameters obtained using the Network Analyzer coupled with the Air Coax Test Fixture. The results are shown in FIGS. 15-20 , illustrating the dielectric constant vs. the frequency and the loss tangent vs. the frequency, respectively, of Comparative Example C6 (1501, 1601), Comparative Example C7 (1502, 1602), Example 11 (1701, 1801), Example 12 (1702, 1802), Example 13 (1901, 2001), and Example 14 (1902, 2002).

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